Polyazole-based polymer films

Abstract

The present invention relates to polymer films and a polymer membrane having an improved mechanical property profile produced therefrom, to a process for producing them and to their use. The polymer films, polymer membranes and separation membranes of the invention are produced from selected polymer raw materials and have excellent chemical, thermal and mechanical properties as are required for use as polymer electrolyte membranes (PEMs) in PEM fuel cells or in apparatuses for the filtration and/or separation of gases and/or liquids or for reverse osmosis.

1 . A polymer film based on polyazoles which is obtainable by a process comprising steps 
 A) dissolving the polyazole polymer in polar, aprotic organic solvent,    B) casting a polymer film using the solution obtained from Step A),    C) drying the film formed in step B) until it is self-supporting, wherein a polyazole polymer powder having a particle size in the range from 300 μm to 1500 μ is used in step A).    
     
     
         2 . A polymer film as claimed in  claim 1 , wherein a polyazole polymer powder having a particle size in the range from 300 μm to 1250 μm, in particular from 300 μm to 1000 μm, particularly preferably from 500 μm to 1000 μm, is used.  
     
     
         3 . A polymer film as claimed in  claim 1 , wherein the polyazole-based polymer used is a polymer comprising recurring azole units of the formula (I) and/or (II)  
       
         
           
           
               
               
           
         
       
       where 
 Ar are identical or different and are each a tetravalent aromatic or heteroaromatic group which can be monocyclic or polycyclic,  
 Ar 1  are identical or different and are each a divalent aromatic or heteroaromatic group which can be monocyclic or polycyclic,  
 Ar 2  are identical or different and are each a trivalent aromatic or heteroaromatic group which can be monocyclic or polycyclic,  
 X are identical or different and are each oxygen, sulfur or an amino group bearing a hydrogen atom, a group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as further radical.  
 
     
     
         4 . A polymer film as claimed in  claim 3 , wherein the polyazole-based polymer used is a polymer comprising recurring benzimidazole units of the formula (III)  
       
         
           
           
               
               
           
         
       
       wherein n is an integer greater than or equal to 10, preferably greater than or equal to 100.  
     
     
         5 . A polymer film as claimed in  claim 1 , wherein drying of the film in step C) is carried out at temperatures in the range from room temperature to 300° C.  
     
     
         6 . A polymer film as claimed in  claim 1 , wherein drying of the film in step C) is carried out for a period of from 10 seconds to 24 hours.  
     
     
         7 . A doped polymer membrane based on polyazoles which is obtainable by a process comprising the steps 
 A) dissolving the polyazole polymer in a polar, aprotic organic solvent,    B) casting a polymer film using the solution obtained from step A),    C) drying the film formed in step B) until it is self-supporting,    D) doping the polymer film obtained in step C) with a dopant, wherein a polyazole polymer powder having a particle size in the range from 300 μm to 1500 μm is used in step A).    
     
     
         8 . A polymer membrane as claimed in  claim 7 , wherein a polyazole polymer powder having a particle size in the range from 300 μm to 1250 μm, in particular from 300 μm to 1000 μm, particularly preferably from 500 μm to 1000 μm, is used.  
     
     
         9 . A polymer membrane as claimed in  claim 7 , wherein the polyazole-based polymer used is a polymer comprising recurring azole units of the formula (I) and/or (II)  
       
         
           
           
               
               
           
         
       
       where 
 Ar are identical or different and are each a tetravalent aromatic or heteroaromatic group which can be monocyclic or polycyclic,  
 Ar 1  are identical or different and are each a divalent aromatic or heteroaromatic group which can be monocyclic or polycyclic,  
 Ar 2  are identical or different and are each a trivalent aromatic or heteroaromatic group which can be monocyclic or polycyclic,  
 X are identical or different and are each oxygen, sulfur or an amino group bearing a hydrogen atom, a group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as further radical.  
 
     
     
         10 . A polymer membrane as claimed in  claim 7 , wherein the polyazole-based polymer used is a polymer comprising recurring benzimidazole units of the formula (III)  
       
         
           
           
               
               
           
         
       
       where n is an integer greater than or equal to 10, preferably greater than or equal to 100.  
     
     
         11 . A polymer membrane as claimed in  claim 7 , wherein drying of the film in step C) is carried out at temperatures in the range from room temperature to 300° C.  
     
     
         12 . A polymer membrane as claimed in  claim 7 , wherein drying of the film in step C) is carried out for a period of from 10 seconds to 24 hours.  
     
     
         13 . A polymer membrane as claimed in  claim 7 , wherein doping is carried out for a period of from 5 minutes to 96 hours.  
     
     
         14 . A polymer membrane as claimed in  claim 7 , wherein the degree of doping is from 3 to 15 mol of acid per mol of repeating units of the polymer.  
     
     
         15 . A polymer membrane as claimed in  claim 7 , wherein the dopant used is sulfuric acid or phosphoric acid.  
     
     
         16 . A membrane-electrode unit comprising at least one polymer membrane as claimed in  claim 7  and at least one electrode.  
     
     
         17 . A polymer electrolyte fuel cell comprising at least one membrane-electrode unit as claimed in  claim 16 .  
     
     
         18 . A polyazole-based separation membrane obtainable by a process comprising the steps 
 A) dissolving the polyazole polymer in a polar, aprotic organic solvent,    B) casting a polymer film using the solution obtained from step A),    C) dipping this film into a precipitation bath wherein a polyazole polymer powder having a particle size in the range from 300 μm to 1500 μm is used in step A).    
     
     
         19 . A separation membrane as claimed in  claim 18 , wherein a polyazole polymer powder having a particle size in the range from 300 μm to 1250 μm, in particular from 300 μm to 1000 μm, particularly preferably from 500 μm to 1000 μm, is used.  
     
     
         20 . The use of a separation membrane as claimed in  claim 19  for the filtration and/or separation of gases and/or liquids or in reverse osmosis.  
     
     
         21 . An apparatus for the filtration and/or separation of gases and/or liquids comprising at least one separation membrane as claimed in  claim 18 .  
     
     
         22 . An apparatus for carrying out reverse osmosis comprising at least one separation membrane as claimed in  claim 18.